Processes for transalkylating aromatic hydrocarbons

ABSTRACT

A process for transalkylating aromatic hydrocarbon compounds, the process comprising introducing an aromatic hydrocarbon feed stream and a water source to a transalkylation zone. The feed stream contacts a catalyst in the transalkylation zone in the presence of water, and produces a reaction product stream comprising benzene and xylene. The invention includes methods to control the transalkylation process.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Division of prior U.S. application Ser. No.12/894,204 which was filed on Sep. 30, 2010 now U.S. Pat. No. 8,242,321,the contents of which are incorporated herein by reference thereto.

FIELD OF THE INVENTION

The present invention generally relates to improved processes fortransalkylating aromatic hydrocarbon compounds. More particularly theinvention relates to aromatic transalkylation processes producingxylenes and benzene.

DESCRIPTION OF RELATED ART

Xylene isomers (“xylenes”) and benzene are produced in large volumesfrom petroleum by the reforming of naphtha. However, neither the xylenesnor benzene are produced in sufficient volume to meet demand.Consequently, other hydrocarbons are necessarily converted to increasethe yield of the xylenes and benzene via processes such astransalkylation, disproportionation, isomerization, and dealkylation.For example, toluene commonly is dealkylated to produce benzene.Alternatively, or additionally, toluene can be disproportionated toyield benzene and C₈ aromatics from which the individual xylene isomersare recovered.

More recently, development has been directed at selectivelytransalkylating heavier aromatics, such as C₉+ aromatics, with tolueneand/or benzene to increase the yield of xylenes and benzene fromaromatics complexes. In this regard, a variety of catalysts have beendeveloped for these processes. For example, a wide range of zeolites,including mordenite, have been disclosed as effective transalkylationcatalysts. Shaped catalysts, multiple zeolites, metal modifiers, andtreatments such as steam calcination have been described as increasingthe effectiveness of the catalysts.

Known catalysts are effective for producing xylenes and benzene.Specifically, catalysts having a sufficient metal function are suitableto convert heavier aromatics, such as C₉+ aromatics to xylenes andbenzene and provide improved catalyst stability in a transalkylationprocess. However, in transalkylation processes employing such catalysts,aromatic rings may become saturated or even cleaved resulting innaphthene and acyclic paraffin (non-aromatics) co-production, which canresult in a loss of valuable aromatics. Also, because some of thenon-aromatics have similar boiling points to benzene (benzeneco-boilers), they are not readily removed to achieve a benzene producthaving a desired purity for commercial applications. Although thebenzene co-boilers can be fractionated or extracted with a solvent, suchprocesses are expensive and typically require additional equipment.

Accordingly, it is desirable to provide a transalkylation process thatproduces a high purity benzene product. In another aspect, it isdesirable to provide a transalkylation process to that produces lessbenzene co-boilers. Other desirable features and characteristics of thepresent invention will become apparent from the subsequent detaileddescription of the invention and the appended claims.

SUMMARY OF THE INVENTION

It has been discovered that introducing water into a transalkylationzone reduces the production of benzene co-boilers and/or improves thepurity of the benzene fraction of the transalkylation reaction productstream. In another aspect, the invention enables control of the purityof a benzene product stream and/or control of the amount of benzeneco-boilers relative to benzene in the reaction product stream orfraction thereof.

In an embodiment, the invention is a process for transalkylatingaromatic hydrocarbon compounds comprising introducing a water source andthe aromatic hydrocarbon compounds to the transalkylation zone. The feedstream is contacted with a catalyst in the transalkylation zone undertransalkylation conditions including the presence of water. A reactionproduct stream comprising benzene and xylene is produced. In anexemplary embodiment, the catalyst comprises an aluminosilicate zeolitecomponent having an MOR framework type, an MFI molecular sieve componenthaving a Si/Al₂ molar ratio of less than 80, an inorganic oxide binder,and a metal component comprising a metal selected from the groupconsisting of rhenium, nickel, cobalt, molybdenum, tungsten, tin,germanium, lead, indium, platinum, palladium, and combinations thereof.

In another embodiment, the invention is a method for controlling anaromatic transalkylation process comprising introducing aromatichydrocarbon compounds and a water source to a transalkylation zone.Contacting the feed stream with a catalyst in the transalkylation zoneunder transalkylation conditions including the presence of water.Producing a benzene product stream, determining a purity of the benzeneproduct stream, and controlling the introduction of the water source inresponse to the purity of the benzene product stream.

DETAILED DESCRIPTION

The aromatic hydrocarbons to be transalkylated by processes of theinvention include alkylaromatic hydrocarbons of the general formulaC₆H_((6-n))R_(n), where n is an integer from 0 to 5 and R is CH₃, C₂H₅,C₃H₇, or C₄H₉, in any combination. Non-limiting examples include:benzene, toluene, ethylbenzene, ethyltoluenes, propylbenzenes,tetramethylbenzenes, ethyl-dimethylbenzenes, diethylbenzenes,methylethylbenzenes, methylpropylbenzenes, ethylpropylbenzenes,triethylbenzenes, trimethylbenzenes, di-isopropylbenzenes, and mixturesthereof. The feed stream may comprise lower levels of ortho-xylene,meta-xylene, and para-xylene that are desired products of the process.

As used herein, the term “transalkylation” encompasses transalkylationbetween and among alkyl aromatics, between benzene and alkyl aromatics,and it includes dealkylation and disproportionation, e.g., of toluene tobenzene and xylene. The aromatic hydrocarbons also may comprisenaphthalene and other C₁₀ and C₁₁ aromatics. Herein, hydrocarbonmolecules may be abbreviated C₁, C₂, C₃, . . . C_(n), where “n”represents the number of carbon atoms in the hydrocarbon molecule. Suchabbreviations followed by a “+” is used to denote that number of carbonatoms or more per molecule, and a “−” is used to denote that number ofcarbon atoms or less per molecule.

Polycyclic aromatics having from 2 to 4 rings are permitted in the feedstream of the present invention. Non-limiting examples include: indanes,naphthalenes, tetralins, decalins, biphenyls, diphenyls and fluorenes.Indane is meant to define a nine carbon atom aromatic species with onering of six carbon atoms and one ring of five carbon atoms wherein twocarbon atoms are shared. Naphthalene is meant to define a ten carbonatom aromatic species with two rings of six carbon atoms wherein twocarbon atoms are shared.

The aromatic hydrocarbons to be transalkylated may be introduced to thetransalkylation zone in one or more feed streams. As used herein, theterm “zone” can refer to one or more equipment items and/or one or moresub-zones. Equipment items may include, for example, one or morevessels, heaters, separators, exchangers, conduits, pumps, compressors,and controllers. Additionally, an equipment item can further include oneor more zones or sub-zones. In embodiments having multiple feed streams,the feed streams may be introduced separately to the transalkylationzone, or two or more of the feed streams may be combined in any mannerprior to passing them into the transalkylation zone.

The feed streams may be derived from one or more sources including,without limitation, catalytic reforming, pyrolysis of naphtha,distillates or other hydrocarbons to yield light olefins and heavieraromatics-rich byproducts, and catalytic or thermal cracking of heavyoils to yield products in the gasoline range. Products from pyrolysis orother cracking operations generally will be hydrotreated according toprocesses well known in the industry before being charged to thetransalkylation zone in order to remove sulfur, olefins and othercompounds which would affect product quality. Light cycle oil also maybe beneficially hydrocracked to yield lighter components which can bereformed catalytically to yield the aromatics-rich feed stream. If thefeed stream is catalytic reformate, the reformer preferably is operatedat high severity for high aromatics yield with a low concentration ofnon-aromatics in the product. The reformate may also be subjected toolefin saturation to remove potential product contaminants and materialsthat could polymerize to heavy non-convertibles in a transalkylationprocess. Such processing steps are described in U.S. Pat. No. 6,740,788B1, which is incorporated herein by reference thereto.

A feed stream can include a substantially pure alkylaromatic hydrocarbonof from about 6 to about 15 carbon atoms, a mixture of suchalkylaromatic hydrocarbons, or a hydrocarbon fraction rich in saidalkylaromatics. A feed stream also may contain lesser concentrations ofnon-aromatics such as pentanes, hexanes, heptanes and heavier paraffinsalong with paraffins along with methylcyclopentane, cyclohexane andheavier naphthenes; pentanes and lighter paraffins generally will havebeen removed before processing. The combined transalkylation feedpreferably contains no more than about 10 wt % non-aromatics; andolefins preferably are restricted to a Bromine Index of no more thanabout 1000, and preferably no more than about 500.

In an embodiment, at least two feed streams are introduced to thetransalkylation zone, a light feed stream and a heavy feed stream. Thelight aromatic feed stream may comprise at least one of benzene andtoluene. Preferred components of the heavy aromatic feed are C₉+aromatics, thereby effecting transalkylation of toluene and C₉+aromatics to yield additional xylenes. Benzene may also betransalkylated to yield additional toluene. Indane may be present in theheavy aromatics feed stream although it is not a desirable component toeffect high yields of xylenes in the transalkylation zone effluent. C₁₀+aromatics also may be present, preferably in an amount of 30% or less ofthe heavy aromatic feed. The heavy aromatic feed stream preferablycomprises at least about 90 mass % aromatics, and may be derived fromthe same or different known refinery and petrochemical processes as thebenzene/toluene feed stream and/or may be recycled from the separationof the transalkylation effluent.

The aromatic feed to a transalkylation reaction zone is usually firstheated by indirect heat exchange against the reaction product stream andthen is heated to reaction temperature by exchange with a warmer stream,steam or a furnace. The feed is preferably transalkylated in the vaporphase and in the presence of hydrogen. In an embodiment a hydrogenstream is introduced to the transalkylation zone. The hydrogen streammay comprise other compounds, e.g. C₁ to C₄ hydrocarbons, in addition tohydrogen. Hydrogen and hydrocarbons may be recycled in the process asdescribed below. If present, free hydrogen is associated with thefeedstock and recycled hydrocarbons, if any, in an amount from about 0.1moles per mole of aromatics up to 10 moles per mole of aromatics. Thisratio of hydrogen to aromatics is also referred to as hydrogen tohydrocarbon ratio.

The feed then is passed through one or more reactors containing thetransalkylation catalyst to produce a reaction product stream comprisingunconverted feed and product hydrocarbons including xylenes and benzene.This reaction product stream is normally cooled by indirect heatexchange against the aromatic feed stream entering the transalkylationzone and may be further cooled through the use of air or cooling water.The reaction product stream may be separated e.g. in a vapor-liquidseparator to produce a vapor phase hydrogen stream and a liquid phasereaction product stream. The vapor phase hydrogen stream includeshydrogen and light hydrocarbons which may be recycled and combined withthe feed as described above. The liquid phase reaction product streammay be passed into a stripping column in which substantially all C5 andlighter hydrocarbons present are concentrated into an overhead streamand removed from the process. As used herein, the term “substantiallyall” means an amount generally of at least 90%, preferably at least 95%,and optimally at least 99%, by weight, of a compound or class ofcompounds in a stream. The stripping column also produces a net stripperbottoms stream, which is referred to herein as the transalkylation zoneeffluent.

The transalkylation zone effluent may be further separated in adistillation zone comprising at least one distillation column to producea benzene product stream. Various flow schemes and combinations ofdistillation columns to separate transalkylation zone effluent viafractional distillation are well known in the art. In addition to thebenzene product stream, the distillation zone may produce a tolueneproduct stream, and a C₈+ product stream. See, e.g., U.S. Pat. No.7,605,295. It is also known that the transalkylation zone strippercolumn may be designed and operated to produce a benzene product stream.See, e.g., U.S. Pat. No. 6,740,788. Thus, the reaction product streamcontains a benzene fraction that may be separated by fractionaldistillation to produce a benzene product stream.

In another embodiment, the transalkylation effluent is separated into alight recycle stream, a mixed C₈ aromatics product, and a heavy aromaticproduct stream in a distillation zone. The mixed C₈ aromatic product maybe sent for recovery of para-xylene and/or other isomers. The lightrecycle stream may be diverted to other uses such as benzene and toluenerecovery, but may be recycled, in part, to the transalkylation zone. Theheavy recycle stream contains substantially all of the C₉ and heavieraromatics and may be partially or totally recycled to thetransalkylation reaction zone.

The invention also requires introducing a water source into thetransalkylation zone. The water source may be introduced as a separatestream into the transalkylation zone, and/or the water source may becombined with an aromatic feed stream and/or a hydrogen containingstream. The water source may comprise water or other compoundscontaining oxygen that will decompose to produce water in thetransalkylation zone. Typical examples of water sources, include withoutlimitation, any alcohol, aldehyde, epoxide, ketone, phenol, and ether.Preferably, the water source has a molecular weight or boiling pointwithin the range of molecular weights or boiling points of thehydrocarbons in the feed or hydrogen containing streams. The watersource may comprise methanol, ethanol, propanol ethyl ether, methyltert-butyl ether, isopropyl ether, and tertiary butyl alcohol.

In an embodiment, the water source is introduced to the transalkylationzone in an amount to provide more than 100 ppm-wt of water based uponthe mass of the feed stream. The amount of water provided by a watersource is the amount of water that would result from the water sourceconverting to water in the process. The amount of water provided by awater source is readily determined by one of ordinary skill in the art.The mass of a water source and the mass of the feed are used todetermine the amount of water source, e.g. ppm-wt based on the mass ofthe feed. This value is multiplied by a factor equal to the weight ofwater that would be produced per weight of water source converted toobtain the amount of water provided by the water source based upon themass of the feed. The factor is 0.56 for methanol (CH₃OH) and 0.58 forethylene glycol (C₂H₄(OH)₂).

In another embodiment, the water source is introduced to thetransalkylation zone in an amount to provide at least about 125 ppm-wtof water, and may provide at least about 150 ppm-wt, and optionally atleast about 300 ppm-wt of water based upon the mass of the feed stream.In a further embodiment, the water source is introduced to thetransalkylation zone in an amount to provide from more than 100 ppm-wtof water to about 1000 ppm-wt of water based upon the mass of the feedstream. In another embodiment the water source is introduced to thetransalkylation zone in an amount to provide from at least about 125ppm-wt to about 1000 ppm-wt, and may provide from at least about 150ppm-wt to about 800 ppm-wt of water based upon the mass of the feedstream.

The aromatic feed stream introduced into the transalkylation zonecontacts the catalyst at transalkylation conditions to produce thereaction product stream which comprises comprising unconverted feed,xylenes, and benzene. The transalkylation conditions include thepresence of water. In an embodiment, the water is in the vapor phase.Without wishing to be bound by any particular theory, it is believedthat the water modifies or attenuates the metal function of the catalystto reduce the amount of benzene co-boilers that would otherwise beproduced, thus increasing the purity of the benzene fraction of thereaction product stream. As used herein the term “benzene co-boilers”means non-aromatic hydrocarbon compounds having 6 or 7 carbon atoms permolecule. Benzene co-boilers that are particularly difficult to separatefrom benzene by fractional distillation include cyclohexane;methylcyclopentane; 2,3-dimethylpentane; 3-methylhexane; anddimethylcyclopentane.

The water source may be introduced into the transalkylation zonecontinuously at a constant rate, or the rate of water source additionmay vary during the process cycle, e.g. as the feed quality varies, asthe catalyst deactivates, and as processing objectives such as thedegree of conversion change. A process cycle runs from the initialintroduction of feed until the process is discontinued to regenerate orreplace the catalyst. A process cycle may be measured in a variety ofways including: time on stream (i.e. time feed is being introduced); thequantity of feed that has been introduced, e.g. mass or volume of feedprocessed; and the quantity of feed (mass or volume) per quantity ofcatalyst (mass or volume), e.g. barrels (feed) per pound (catalyst)(BPP), cubic meters of feed (e.g. at standard or normal conditions) permass or volume of catalyst. A process cycle may be temporarily suspendedor halted by discontinuing feed introduction. If suspended for anextended period of time, the unit may be held in a stand-by mode.However, the length of the process cycle will continue to accrue oncefeed introduction resumes, provided the catalyst has not beenregenerated or replaced. In another embodiment, the water source isadded intermittently during the process cycle.

In a further embodiment, the water source is introduced when the feed isinitially introduced to the transalkylation zone. During the initialportion of the process cycle, the catalyst usually exhibits the highestactivity; therefore, the operating temperatures are usually at aminimum. These conditions typically result in higher amounts of benzeneco-boilers and lower benzene purity. The catalyst ages and deactivatesas the process cycle continues and to maintain the desired level ofconversion the reactor temperature may be increased. The amount of watersource addition may be decreased as the process cycle continues and thereaction temperature increases. Without wishing to be bound by anyparticular theory, it is believed that benzene co-boilers are crackedmore efficiently by the acid sites on the catalyst, especially the MFIzeolite, as the temperature increases. At some point in the processcycle, water source introduction may no longer be required, e.g. toobtain the desired benzene product purity.

In an embodiment, the water source is introduced intermittently orcontinuously during the initial one-third of the process cycle. Inanother embodiment, the water source is introduced intermittently orcontinuously during the initial one-fifth (20%) of the process cycle;and the water source may be introduced intermittently or continuouslyduring the initial one-tenth (10%) of the process cycle. To determine aportion or fraction of a process cycle herein, the process cycle and thefraction thereof are determined on the basis of mass of feed per mass ofcatalyst, e.g. metric ton of feed per metric ton of catalyst.

In an embodiment, the purity of the benzene product may be controlled byadjusting the rate of water source introduced in response to adetermination of the benzene product purity. Benzene purity may bedetermined by analysis of the benzene product stream and/or from adetermination of the amount of benzene co-boilers relative to the amountof benzene. For example, the amount of benzene co-boilers relative tothe amount of benzene may be determined in any of the reaction productstream, the transalkylation zone effluent stream, and the benzeneproduct stream. The determination of benzene purity and the relativeamount of the benzene co-boilers may be performed by manually obtainingsamples and analyzing them off-line or by automatic on-line analysis.Changing the rate of water source introduction in response to thedetermination may be done manually or through the use of a controlsystem as is known in the art. The manual and automatic modes of thesesteps may be combined in any manner. For example, an on-line analyzermay determine the amount of benzene co-boilers relative to the amount ofbenzene in the reaction product stream and send a signal to a processcontroller. The process controller may in turn send a signal to acontrol valve that regulates the rate of water source addition.Algorithms, such as to convert the relative amount of co-boilers to apurity of the benzene product steam may include terms to account for thefractional distillation efficiency and/or time lags in the process, andmay be applied in or by any of the analyzer, controller, and controlvalve to generate or interpret the signals. Such techniques are wellknown in the art of process control.

Contacting the feed and water with the catalyst can be effected in anyconventional or otherwise convenient manner and may occur as a batch orcontinuous type of operation. In an embodiment, the catalyst is disposedin one or more fixed beds in a reaction zone of a vertical reactor withthe aromatic feed and water charged through the bed in an upflow ordownflow manner. Transalkylation conditions may include a temperature ina range of from about 200° C. to about 540° C., preferably between about200° C. to about 480° C.; a pressure in a range of from about 100 kPa toabout 6 MPa absolute; and a weight hourly space velocity (WHSV, i.e.,weight of aromatic feed introduced per weight of catalyst per hour) in arange of from about 0.1 to about 20 hr⁻¹.

In an embodiment, the invention includes a transalkylation catalystcomprising: an aluminosilicate zeolite having an MOR framework type, anMFI molecular sieve having a Si/Al₂ molar ratio of less than 80, a metalcomponent comprising a metal selected from the group consisting ofrhenium, nickel, cobalt, molybdenum, tungsten, tin, germanium, lead,indium, platinum, palladium, and combinations thereof, and an inorganicoxide binder.

Aluminosilicate zeolite having an MOR framework is described in ATLAS OFZEOLITE FRAMEWORK TYPES, 6th Revised Edition, C. H. Baerlocher, L. B.McCusker, and D. H. Olson, editors, Elsevier (2007), pp. 218-219. TheMOR framework comprises four- and five-membered rings of SiO₄ and AlO₄tetrahedra to form a crystal lattice comprising 12-ring channels runningparallel along a crystal axis to give a tubular configuration. In anembodiment, the aluminosilicate zeolite having an MOR frameworkcomprises mordenite. Where mordenite is a component of the catalyst, themordenite preferably has a Si/Al₂ molar ratio of less than about 40. TheSi/Al₂ molar ratio of mordenite in an embodiment is less than about 25,and in another embodiment the mordenite Si/Al₂ molar ratio is betweenabout 15 and about 25. Mordenite may be synthesized with a Si/Al₂ molarratio of between about 10 and about 20. Mordenite is preferably at leastpartially in the hydrogen form and/or may be dealuminated by a varietyof techniques, e.g. steaming, and acid extraction of aluminum toincrease the Si/Al₂ ratio of the mordenite.

In another embodiment, the aluminosilicate zeolite having an MORframework comprises UZM-14. UZM-14 is described in U.S. Pat. No.7,687,423, which is incorporated herein by reference in its entirety.UZM-14 comprises globular aggregates of crystallites having a MORframework type comprising 12-ring channels, and one or more of thefollowing distinctive characteristics: a mesopore volume of at leastabout 0.10 cc/gram, preferably at least about 0.13 cc/gram, morepreferably at least about 0.2 cc/gram; a mean crystallite lengthparallel to the direction of the 12-ring channels of about 60 nm orless, preferably about 50 nm or less; a Si/Al₂ mole ratio of betweenabout 8 and about 50, and preferably is no more than about 30; and atleast about 1×10¹⁹ 12-ring channel openings per gram of UZM-14 material.

In an embodiment, UZM-14 comprises globular aggregates of crystalliteshaving a MOR framework type comprising 12-ring channels, asilica-alumina mole ratio of from about 8 to no more than about 30, amesopore volume of at least about 0.10 cc/gram, and a mean crystallitelength parallel to the direction of the 12-ring channels of about 60 nmor less.

UZM-14 has an empirical composition in the as-synthesized form on ananhydrous basis expressed by the empirical formula:M_(m) ^(n+)R_(r) ^(p+)Al_(1-x)Si_(y)O_(z)where M is at least one exchangeable cation and is selected from thegroup consisting of alkali and alkaline earth metals including but notlimited to lithium, sodium, potassium, rubidium, cesium, calcium,strontium, barium and mixtures thereof. R is at least one organic cationselected from the group consisting of protonated amines, protonateddiamines, quaternary ammonium ions, diquaternary ammonium ions,protonated alkanolamines, and quaternized alkanolammonium ions. Relatingthe components, “m” is the mole ratio of M to Al and varies from about0.05 to about 0.95; “r” is the mole ratio of R to Al and has a value ofabout 0.05 to about 0.95; “n” is the weighted average valence of M andhas a value of about 1 to about 2; “p” is the weighted average valenceof R and has a value of about 1 to about 2; “y” is the mole ratio of Sito Al and varies from about 3 to about 50; and “z” is the mole ratio ofO to Al and has a value determined by the equation: z=(m·n+r·p+3+4y)/2.

The catalyst also includes an MFI molecular sieve having a Si/Al₂ molarratio of less than 80. Zeolites having an MFI type framework aredescribed in ATLAS OF ZEOLITE FRAMEWORK TYPES, 6th Revised Edition, C.H. Baerlocher, L. B. McCusker, and D. H. Olson, editors, Elsevier(2007). MFI type zeolites have a 3-dimensional 10-ring channel system:[100] 10-MR 5.1×5.5 Å and [010] 10-MR 5.3×5.6 Å. In an embodiment, MFImolecular sieves used in the catalysts of this invention have a Si/Al₂molar ratio of less than about 40, preferably less than about 25, forexample, between about 15 to about 25. An example of a suitable MFImolecular sieve for inclusion in the catalyst includes, but is notlimited to, ZSM-5, which is disclosed in U.S. Pat. No. 3,702,886,incorporated herein, by reference thereto. Suitable MFI molecular sievesare also available, for example, from Zeolyst International ofConschocken, Pa. and Tosoh Corporation of Tokyo, Japan.

In an embodiment, the MFI molecular sieve has a “Total Acidity” of atleast about 0.15, preferably at least about 0.25, and more preferably atleast about 0.4, for example, 0.4 to 0.8. Total Acidity is determined byAmmonia Temperature Programmed Desorption (Ammonia TPD). The TotalAcidity of the MFI molecular sieve may be that of the MFI to be used inmaking the catalyst of the invention or may be achieved during thepreparation of the catalyst. Typically, the MFI molecular sieve is atleast partially in the hydrogen form in the finished catalyst. TheAmmonia TPD process involves first heating a sample (about 250milligrams) of molecular sieve at a rate of about 5° C. per minute to atemperature of about 550° C. in the presence of a 20 volume percentoxygen in helium atmosphere (flow rate of about 100 milliliters perminute). After a hold of about one hour, helium is used to flush thesystem (about 15 minutes) and the sample is cooled to about 150° C. Thesample is then saturated with pulses of ammonia in helium at about 40milliliters per minute. The total amount of ammonia used is greatly inexcess of the amount required to saturate all the acid sites on thesample. The sample is purged with helium (about 40 milliliters perminute) for about 8 hours to remove physically adsorbed ammonia. Withthe helium purge continuing, the temperature is increased at a rate ofabout 10° C. per minute to a final temperature of 600° C. The amount ofammonia desorbed is monitored using a calibrated thermal conductivitydetector. The total amount of ammonia is found by integration. Dividingthe total amount of ammonia by the dry weight of the sample yields theTotal Acidity. As used herein, values of Total Acidity are given inunits of millimoles of ammonia per gram of dry sample.

The inorganic oxide binder of the catalyst comprises such materials asalumina, silica, zirconia, titania, thoria, boria, magnesia, chromia,stannic oxide, and the like as well as combinations and compositesthereof, for example silica-alumina, alumina-zirconia, alumina-titania,aluminum phosphate, and the like. Alumina is a preferred refractoryinorganic oxide binder. As is well known in the art, a precursor of thedesired refractory inorganic oxide may be used to form, bind, and/orotherwise prepare the catalyst. Such binder precursors or sources may beconverted into a refractory inorganic oxide binder, e.g. by calcination.The alumina may be any of the various aluminum oxides, hydroxides, andgels, including boehmite, pseudo-boehmite, gibbsite, bayerite, and thelike, especially transition and gamma aluminas. Suitable aluminas arecommercially available, e.g. under the trade names CATAPAL B and VERSAL250.

The metal component of the catalyst comprises a metal selected from thegroup consisting of rhenium, nickel, cobalt, molybdenum, tungsten, tin,germanium, lead, indium, platinum, palladium, and combinations thereof.In an embodiment, metal component comprises a metal selected from thegroup consisting of rhenium, molybdenum, tin, germanium, indium,platinum, palladium, and combinations thereof. In an embodiment themetal content of the catalyst ranges from about 0.01 wt % to about 10.0wt % as the metal based upon the total weight of the catalyst.

The metal component may be incorporated into the catalyst in anysuitable manner such as comulling, coprecipitation or cogellation withthe carrier material, ion exchange, or impregnation. The metal componentmay exist within the final catalyst as a compound such as an oxide,sulfide, halide, or oxyhalide, in chemical combination with one or moreof the other ingredients of the composite, or as an elemental metal. Onemethod of preparing the catalyst involves the use of a water-soluble orsolvent-soluble, decomposable compound of the metal to impregnate themolecular sieve-containing support. Alternatively, a metal compound maybe added at the time of compositing the molecular sieve component andbinder.

The weight ratio of the MFI molecular sieve component to thealuminosilicate zeolite having the MOR framework may range from about1:10 to 5:1, preferably from about 1:10 to 2:1. In an embodiment, thealuminosilicate zeolite component having the MOR framework comprisesfrom about 20 wt % to about 80 wt % of the catalyst, the MFI molecularsieve component comprises from about 10 wt % to about 70 wt % of thecatalyst, and the inorganic oxide binder comprises between about 1 wt %and about 40 wt % of the catalyst.

The catalyst may optionally include an additional molecular sievecomponent preferably selected from one or more of MEL, EUO, FER, MFS,MTT, MTW, MWW, MAZ, TON and FAU (IUPAC Commission on ZeoliteNomenclature) and UZM-8 (see U.S. Pat. No. 6,756,030 which is hereinincorporated by reference in its entirety). The catalyst may optionallyinclude a fluoride component in an amount ranging from about 0.1 wt % toabout 5.0 wt % of fluoride based upon the total weight of the catalyst.The fluoride component may be incorporated into the catalyst by anyknown technique, e.g. impregnation.

The techniques used to prepare the catalyst are well known to those ofordinary skill in the art. The catalyst can be formed by combining thealuminosilicate zeolite component having the MOR framework, the MFImolecular sieve component, and the inorganic oxide binder and/or aprecursor thereof in any conventional or otherwise convenient manner toform spheres, pills, pellets, granules, extrudates, or other suitableparticle shapes. For example, finely divided aluminosilicate zeolitehaving the MOR framework and MFI molecular sieve particles, and metalsalt particles can be dispersed in an alumina sol, and the mixture inturn dispersed as droplets in a hot oil bath whereby gelation occurswith the formation of spheroidal gel particles. A preferred methodcomprises mixing a finely divided form of the selected aluminosilicatezeolite having the MOR framework and MFI molecular sieve particles, abinder and/or precursor thereof, with a metal salt and, optionally, alubricant; and compressing the mixture into pills or pellets.Alternatively, and still more preferably, the aluminosilicate zeolitehaving the MOR framework, MFI molecular sieve particles, binder and/orprecursor thereof, and metal salt are combined and admixed with apeptizing agent in a mixer-muller, a dilute nitric acid being oneexample of the suitable peptizing agent. The resulting dough can bepressured through a die or orifice of predetermined size to formextrudate particles which can be dried and calcined and utilized assuch. A multitude of different extrudate shapes are possible, including,but not limited to, cylinders, cloverleaf, dumbbell and symmetrical andasymmetrical polylobes, with a trilobe form being favored. Theextrudates also may be formed into spheres by means of a spinning discor drum. The variously formed particles are then usually dried and/orcalcined.

If the metal component is not included in the above forming steps, or ifan additional metal component is to be included, the formed particlesproduced above can be impregnated with a soluble, decomposable compoundcontaining the metal component to form a composite. For example, whenthe metal component comprises molybdenum, typical compounds which may beemployed include ammonium heptamolybdate, alkali metal molybdates (alsoperoxo-, di-, tri-, tetra-, hepta-, octa-, or tetradecamolybdate),molybdic acid, phosphomolybdic acid, Mo—P heteropolyanion compounds,acetyl acetonates, Mo(0) metal, Mo oxides, Mo peroxo complexes, andmixtures thereof. The composite is preferably calcined in an airatmosphere at a temperature of from about 425° C. to about 750° C.,preferably at a temperature of from about 475° C. to about 600° C., overa period of from about 0.5 to about 10 hours. Typically, the formedparticles are also calcined at similar conditions prior to theimpregnation step. The catalyst preparation may include various optionalsteps such as drying and steaming which are well known in the art.

Example 1

A catalyst was prepared by blending of UZM-14, MFI zeolite, and CatapalB to obtain a 50% UZM-14, 25% MFI zeolite, and 25% Catapal B mixture ona volatile free (VF) weight basis. The mixture also included a solutionof ammonium heptamolybdate to obtain 0.5 wt % molybdenum (VF) in thefinal catalyst, and a solution of diluted nitric acid as the peptizingagent to form a dough. The dough was extruded as a cylinder and thecatalyst was calcined at 500° C. for 2 hours in dry air. The UZM-14zeolite used in this example was prepared according to Example 1 of U.S.Pat. No. 7,687,423. Prior to incorporation in the catalyst, the UZM-14was ion exchanged with an ammonium sulfate solution to reduce the sodiumcontent of the zeolite to less than 0.05 wt % sodium. The ion exchangedUZM-14 zeolite had the following properties: a SiO₂/Al₂O₃ molar ratio of15.9, a BET surface area of 448 m²/g, a micropore volume of 0.21cc/gram, and a mesopore volume of 0.31 cc/gram. The MFI zeolite was CBV2314, a ZSM-5 material with SiO₂/Al₂O₃ of 23, obtained from ZeolystInternational. Catapal B was purchased from Vista Chemical Company. Thefinished catalyst had a BET surface area of 375 m²/g, a total porevolume of 0.43 cc/g and a piece density of 1.232 g/cc.

Example 2

The catalyst in this example was prepared in the same way as describedin Example 1, except the final catalyst contained 3.0 wt % molybdenum(VF) and a prepared MFI component had a molar SiO₂/Al₂O₃ ratio of 38, aBET surface area of 351 m²/g, a Langmuir surface area of 517 m²/g, amicropore volume of 0.18 cc/gram and a mesopore volume of 0.21 cc/gram.The ion exchanged UZM-14 zeolite used in this example had the followingproperties: a molar SiO₂/Al₂O₃ ratio of 15.9, a BET surface area of 450m²/g, a micropore volume of 0.21 cc/gram and a mesopore volume of 0.29cc/gram. The catalyst had a BET surface area of 355 m²/g and a totalpore volume of 0.37 cc/g. The piece density was 1.246 g/cc.

Example 3

The catalyst in this example was prepared in the same way and from thesame materials as described in Example 1, except the final catalystcontained 5.0 wt % molybdenum (VF) and the extrudates were trilobesrather that cylinders. The catalyst had a BET surface area of 353 m²/gand a total pore volume of 0.40 cc/g. The piece density was 1.107 g/cc.

Example 4

A catalyst was prepared by blending of mordenite, MFI zeolite, andCatapal B to obtain a 50% mordenite, 25% MFI zeolite, and 25% Catapal Bmixture on a volatile free (VF) weight basis. The mixture also includeda solution of ammonium perrhenate to obtain a catalyst with 0.15 wt %rhenium (VF) in the final catalyst, and a solution of diluted nitricacid as the peptizing agent to form a dough. The dough was extruded as acylinder and the catalyst was calcined at 635° C. for 30 minutes in airwith 15 mole % steam. The mordenite zeolite used in this example was CBV21A, purchased from Zeolyst International having a molar SiO₂/Al₂O₃ratio of 20.7, a BET surface area of 401 m²/g, a Langmuir surface areaof 584 m²/g, a micropore volume of 0.20 cc/gram and a mesopore volume of0.08 cc/gram. The MFI component was the same material as used in Example2. The Catapal B was the same material as used in the other examples.The finished catalyst had a BET surface area of 345 m²/g, a total porevolume of 0.39 cc/g and a piece density of 1.229 g/cc.

Example 5

The catalysts of Examples 1-4 were tested in an aromaticstransalkylation test. Prior to testing, the catalysts were sulfidedin-situ as is well known in the art to convert the metals (Mo and Re)and/or their oxides at least partially, to the metal sulfide. Anobjective of catalyst sulfiding is to add a fixed amount of sulfur tothe catalyst. This was accomplished by passing excess dimethyl disulfide(DMDS), equivalent to 150 ppm-wt as sulfur, in the feed over thecatalyst at a temperature of 280° C., a pressure of 1,724 kPa(g), aweight hourly space velocity of 4 and a hydrogen to hydrocarbon ratio of6 for 26 hours. Catalyst sulfiding was continued at a temperature of360° C. for 12 hours, followed by 2 hours at 350° C. This procedureprovides a sulfided catalyst with a relatively fixed sulfur content suchthat longer sulfiding with excess DMDS will not increase the sulfurcontent of the catalyst any further. After the sulfiding procedure wascomplete, feed without a sulfur source was continued to the catalyst for10 hours as transalkylation conditions were lined out for testing. Thefollowing were common to all stages of the test. A pressure of 1,724kPa(g), a weight hourly space velocity of 4 and a hydrogen tohydrocarbon ratio of 6. Product samples were obtained hourly throughoutall stages of the test and were analyzed to determine the benzene puritycalculated as benzene/(benzene+C₆ and C₇ non-aromatics) on a weightpercent basis.

Stage 1 was conducted at 350° C. to establish a base line “dry”performance during the first 10 hours of testing. To ensure the feed hadessentially zero water, the feed for all stages of the test was driedfirst through 3A/13X molecular sieve driers followed by high surfacearea sodium driers. No water source was added in Stage 1. Tertiary-butylalcohol (TBA) was then introduced to the dry feed to provide 150 ppm-wtof water based on the mass of the feed stream to begin Stage 2. After 15hours at these conditions, the TBA was increased to provide 300 ppm-wtof water based on the mass of the feed stream to begin Stage 3. After 7hours at Stage 3 conditions, the TBA was removed from the feed and waterwas purged from the system for about 15 hours when dry steady stateconditions at 350° C. were attained in Stage 4. The reaction temperaturewas then increased to 365° C. and baseline dry data was obtained for 10hours at the higher temperature in Stage 5. TBA was then introduced tothe dry feed for 15 hours in Stage 6 to provide 150 ppm-wt of waterbased on the mass of the feed stream. Finally, the TBA was removed fromthe feed stream to re-establish dry conditions in Stage 7. The feed hadnominally the composition in weight percent given in Table 1. Theresults for the steady state operation of each stage are reported belowin Table 2.

TABLE 1 Toluene 75 Propylbenzene 2.0 Methylethylbenzene 10Trimethylbenzene 9.7 Indane 0.8 Methylpropylbenzene 1.0 Diethylbenzene0.4 Dimethylethylbenzene 1.0 C₁₁+ aromatics 0.1

TABLE 2 Temperature, Water level in Catalyst of Benzene Purity Stage °C. feed, ppm-wt Example # (wt %) 1 350 dry 1 99.75 1 350 dry 2 99.05 1350 dry 3 99.10 1 350 dry 4 98.80 2 350 150 1 99.75 2 350 150 2 99.30 2350 150 3 99.35 2 350 150 4 98.80 3 350 300 1 99.75 3 350 300 2 99.35 3350 300 3 99.35 3 350 300 4 98.80 4 350 dry 1 99.75 4 350 dry 2 98.80 4350 dry 3 98.80 4 350 dry 4 98.70 5 365 dry 1 99.85 5 365 dry 2 99.20 5365 dry 3 99.25 5 365 dry 4 99.25 6 365 150 1 99.85 6 365 150 2 99.50 6365 150 3 99.55 6 365 150 4 99.25 7 365 dry 1 99.85 7 365 dry 2 99.20 7365 dry 3 99.25 7 365 dry 4 99.20

There is no intention to be bound by any theory presented herein. As iswell know to those skilled in the art, water can interact with zeoliticacid sites and attenuate the acidity. However, if that were the casehere, the conversion/cracking of the non-aromatic benzene co-boilersshould be impaired, resulting in lower benzene purity. In contrast, thedata in Table 2 show little to no measurable effect of water on thebenzene purity for the catalysts of examples 1 and 4. More surprisingly,for the catalysts of examples 2 and 3, water clearly increases thebenzene purity. This suggests that the water interacts with the metalfunction instead of the acid function. However, it is believed an effectwould be observed for examples 1 and 4 if the operating conditions werechanged to produce a less pure benzene stream and/or the amount ofrhenium in example 4 were increased.

The data in Table 2 shows the effect of water to be reversible. Asdiscussed above, processes according to the invention may introduce awater source in the earlier portion of a process cycle to improvebenzene purity, for example, when a catalyst is generally more active.As the catalyst ages, the operating temperature is usually increased tomaintain a desired conversion level and the purity of the benzeneproduct improves so that addition of a water source may be reduced ordiscontinued.

1. A method for controlling an aromatic transalkylation process, themethod comprising: introducing a feed stream comprising aromatichydrocarbon compounds to a transalkylation zone; introducing a watersource to the transalkylation zone; contacting the feed stream with asulfided catalyst comprising an aluminosilicate zeolite component havingan MOR framework type selected from the group consisting of UZM-14 andmordenite; an MFI molecular sieve component; an inorganic oxide bindercomprising a material selected from the group consisting of alumina,silica, zirconia, titania, thoria, boria, magnesia, chromia, stannicoxide, and combinations thereof; and between about 3% and about 5%molybdenum in the transalkylation zone under transalkylation conditionsincluding the presence of water; producing a benzene product stream;determining a purity of the benzene product stream; and controlling theintroduction of the water source in response to the purity of thebenzene product stream to obtain a product having a higher purity ofbenzene.
 2. The process of claim 1 wherein the water source isintroduced to the transalkylation zone in an amount to provide more than100 ppm-wt of water based upon the mass of the feed stream.